Exhaust process for the dyeing of synthetic fibre materials

ABSTRACT

Exhaust process for the dyeing of synthetic fibre materials from organic water-immiscible solvents wherein are used as dyestuffs sulphonamide group containing disperse dyestuffs. There are obtained without originating waste waters dyeings with excellent fastness to washing, rubbing, light and sublimation.

This is a division of application Ser. No. 416,867 filed Nov. 19, 1973which is a continuation of Ser. No. 161,282, filed July 9, 1971 and nowabandoned.

The invention relates to an exhaust process for the dyeing of syntheticfibre materials from organic water-immiscible solvents; moreparticularly it concerns an exhaust process for the dyeing of syntheticfibre materials from organic water-immiscible solvents wherein are usedas dyestuffs disperse dyestuffs containing sulphonamide groups.

Organic water-immiscible solvents suitable for the process according tothe invention are those the boiling point of which lies between 40° and170° C, e.g. aromatic hydrocarbons such as toluene, xylene; andhalogenated hydrocarbons, especially aliphatic chlorinated hydrocarbons,such as methylene chloride, chloroform, carbon tetrachloride,1,1-dichloroethane, 1,2-dichloroethane, 1,1,2-trichloroethane,1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane,1-chloropropane, 2-chloropropane, 1,2-dichloropropane,1,1,1-trichloropropane, 1-chlorobutane, 2-chlorobutane,1,4-dichlorobutane, 1-chloro-2-methylpropane, 2-chloro-2-methylpropaneor dichlorohexane; as well as aliphatic fluorinated andfluoro-chlorinated hydrocarbons, such as perfluoro-n-hexane,1,2,2-trifluoro-trichloroethane and trifluoro-pentachloropropane;aromatic chlorinated and fluorinated hydrocarbons, such aschlorobenzene, fluorobenzene, chlorotoluene and benzotrifluoride.

Tetrachloroethylene, trichloroethylene, 1,1,1-trichloroethane and1,1,1-trichloropropane have proved particularly satisfactory. Mixturesof the said solvents can also be used.

The sulphonamide group-containing disperse dyestuffs to be usedaccording to the invention may be based on any type of dyestuffs,provided these contain at least one sulphonamide group. The dyestuffs tobe used according to the invention may belong, for example, to theseries of metal-containing or metal-free mono- or polyazo dyestuffs or(azo)methine dyestuffs; to the series of anthraquinone dyestuffs and ofcondensation products thereof containing more than three fused rings;other suitable dyestuffs are oxazine, nitrodiphenylamine, naphthalicacid, di- and triphenyl-methane dyestuffs; naphtholactum condensationdyestuffs, quinophthalone dyestuffs, and dyestuffs based onnaphthoquinone and naphthoquinonimine; as well as other condensationdyestuffs. In addition to the sulphonamide groups required bydefinition, the dyestuffs may contain other conventional substituents,such as halogen, alkyl, cycloalkyl, aralkyl, aryl, alkoxy, aryloxy,nitro, sulphone, optionally substituted carboxamide groups, optionallysubstituted or acylated amino groups, alkylthio and arylthio, hydroxy,hydroxyalkyloxy, aminoalkyloxy, cyano, cyanoalkyl, and differentlysubstituted alkyl, aryl, aralkyl radicals, and the like.

The dyestuffs contain one or more sulphonamide groups which are linkedto the aromatic nuclei of the basic ring system of the dyestuff itselfor to aryl, aralkyl, or aliphatic groupings in external positions. Thenumber of sulphonamide groups preferably amounts to 1 to 3.

The sulphonamide groups are characterized by the formula ##STR1## inwhich the radicals B and B₁, independently of one another, denotehydrogen or optionally substituted lower alkyl or alkenyl groups, arylradicals or heteroaryl radicals. Furthermore, the radicals B and B₁together may form a ring which may be interrupted by hetero atoms.

Examples of radicals B and B₁ are the methyl, ethyl or trifluoromethylradicals; the β-hydroxy, β-chloro, β-bromo, β-methoxy, β-methylthio,β-methylsulphonyl or β-cyanoethyl groups; or an ethylene or β-chloro- orβ-bromoethylene radical. If B or B₁ stands for an aryl radical, this ispreferably a phenyl radical which may be substituted by one or morehalogen atoms such as fluorine, chlorine or bromine; nitro groups;trifluoromethyl, hydroxy or lower alkoxy radicals; carboxyl orcarboxamide groups; acylamino groups; sulphonamide or loweralkylsulphonyl radicals. Suitable heteroaryl radicals are, for example,the pyridyl, pyrrolyl, pyrimidinyl, furanyl, thienyl or sulpholanylradicals. Examples of rings which may be formed by B and B₁ and may beinterrupted by hetero atoms are the pyrrolidinyl, piperidinyl,morpholinyl, thiomorpholinyl or thiomorpholinyl dioxide rings.

Dyestuffs containing sulphonamide groups are known in large numbers andare prepared by conventional methods in that suitable dyestuffintermediates containing one or more sulphonamide groups linked to thenucleus or in an external position are converted into the desired finalproducts while retaining the sulphonamide groups and, if desired,further conversion reactions are carried out in the latter. Obviously,it is also possible to start from dyestuffs containing one or moresulphonic acid groups and to convert the sulphonic acid groups into thecorresponding amides in the usual way via reactive intermediate stages,such as e.g. the ester and acid chloride. In the case of azo dyestuffs,the usual conversion reactions are diazotisation and coupling; for mostother dyestuffs classes they are condensation reactions.

Examples of suitable azo dyestuffs containing sulphonamide groups arethe following compounds in which the radical ##STR2## may have thefollowing meaning: ##STR3##

Suitable anthraquinone dyestuffs are, for example, those in which one ormore sulphonamide groups stand in the anthraquinone molecule itself orin aryl or alkyl radicals which are linked to the anthraquinone moleculevia bridge members such as amino, ether, thioether, sulphonamide orsulphonylamino groups.

The anthraquinone compounds may have the following constitutions, forexample, the group ##STR4## having the same meaning as above: ##STR5##furthermore, acylation products of amino-anthraquinones, e.g. of theformulae: ##STR6## with sulpho-carboxylic acids of the general formula##STR7##

X = alkylene, arylene, a bivalent heterocyclic radical; or with acompound of the formula ##STR8## and furthermore, the anthraquinonedyestuffs assembled in the following Table:

      ##STR9##      ##STR10##      ##STR11##      ##STR12##      ##STR13##      ##STR14##      ##STR15##      ##STR16##      ##STR17##      ##STR18##     XX      ##STR19##     XXXX      ##STR20##      XXXXXXX      ##STR21##     XXXX      ##STR22##      XX XXX      ##STR23##     XXXXXXX  (NH.sub.2)  (NH.sub.2)      ##STR24##     XXXXXXX      ##STR25##     XXXXXX      ##STR26##      XXXXXX

The anthraquinone dyestuffs of the formula ##STR27## in which

R₁ means an amino group

R₂ means a hydroxy or amino group

X means --O-- or --S--

Y means a phenylene group and

D means ##STR28## have proved to be of special interest and among themthe dyestuffs ##STR29## have proved to be especially valuable.

Among anthraquinone condensation products which contain sulphonamidegroups and contain more than three fused rings, the following may bementioned by way of example: Isothiazoloanthrones, such as ##STR30##Pyrazoloanthrones, such as ##STR31## furthermore, dyestuffs of the type##STR32##

Anthraquinone dyestuffs of the formulae given above are preparedaccording to the synthesis principles known in anthraquinone chemistry.Condensation reactions with appropriate starting compounds are suitablein the first instance for this purpose. For example, aminogroup-containing anthraquinone compounds in which the amino groups standeither in an external position or, preferably, in a position linked tothe nucleus, can be condensed with suitable sulphoaryl-acid halides oranhydrides, e.g. sulphophenyl- or naphthyl-carboxylic acid or -sulphonicacid chlorides or bromides to form the corresponding acid amides; or,for example, anthraquinone compounds with mobile halogen atoms can bereacted with sulphoaryl-amines such as sulphophenyl- orsulphonaphthyl-amines to form the correspondingsulphoarylamino-anthraquinone derivatives, and the free sulpho groupsstill present in the resultant dyestuffs can be converted intosulphonamide groups in known manner. Alternatively, for example,anthraquinone compounds containing amino groups can be condensed withsulphonamido-aryl-acid halides or anhydrides, or e.g. anthraquinonecompounds containing mobile halogen atoms can be condensed withsulphonamido-arylamines.

Anthraquinone ether and thioether derivatives in which sulphonamidegroups are contained in alkyl, aralkyl or aryl radicals of the ether orthioether component, can be prepared according to similar synthesisprinciples. Another possibility of synthetising sulphonamidegroup-containing anthraquinone dyestuffs to be used according to theinvention consists in that anthraquinone-acid halides, such ascarboxylic acid and sulphonic acid chlorides or bromides, are convertedinto the corresponding amides or esters with the aid of suitable aminoor hydroxy compounds which contain at least one additional sulphonamidegroup. Obviously, it is also possible to use for the present processalso those anthraquinone compounds in which one or more sulphonamidegroups stand in a position linked to the nucleus or in whichsulphonamide groups linked to the nucleus as well as externally linkedsulphonamide groups are present.

As representatives of nitro dyestuffs containing sulphonamide groups,there may be mentioned for example dyestuffs of the formula ##STR33## ordyestuffs of the formula ##STR34## in which

R₁ means hydrogen, a halogen atom, a trifluoro, cyano, hydroxy, C₁ -C₄-alkyl or -alkoxy, a hydroxymethyl or -ethyl, a hydroxy-ethylene-oxy,acylamino, alkylsulphonyl-amino, alkylsulphone, carboxamido,aminosulphonyl-alkyleneamino or sulphonamide group;

R₂ means hydrogen or a C₁ -C₄ -alkoxy group;

R₃ means hydrogen, a halogen atom, a hydroxy, hydroxy-ethyleneoxy,carboxamido, aminosulphonyl-alkyleneoxy or sulphonamide group;

X stands for the group --SO₂ -- or --CO; and

Y stands for --NH-- or --O--;

with the proviso that one of the radicals R₁, R₃ or ##STR35## is asulphonamide group or a radical containing a sulphonamide group.

The nitro dyestuff of the formula ##STR36## has proved to be especiallyvaluable.

In many cases it has proved advantageous for the dyebaths to containsmall amounts of water, i.e. up to 1 per cent by weight, preferably 0.5per cent by weight, referred to the weight of the organic solvent.

Furthermore, it has proved expedient in some cases to add non-ionicauxiliaries to the dyebaths. Suitable non-ionic auxiliaries areprimarily the known interface-active ethoxylation and propoxylationproducts of fatty alcohols, alkylphenols, fatty acid amides and fattyacids as well as mixtures thereof; the auxiliaries are used in an amountof 0.05 - 2 per cent by weight, referred to the weight of the organicsolvents. Instead of being immediately added to the dyebaths, theauxiliaries can also be used to advantage for pasting the sulphonamidegroup-containing dyestuffs and in this way be added to the dyebaths inthe form of a dyestuff/auxiliary paste.

The synthetic fibre materials to be dyed according to the invention areprimarily fibre materials of polyesters, such as polyethyleneterephthalate, poly-cyclohexane-dimethylene terephthalate, heterogeneouspolyesters from terephthalic acid, sulphoisophthalic acid and ethyleneglycol, or copolyether ester fibres from p-hydroxybenzoic acid,terephthalic acid and ethylene glycol; cellulose triacetate, cellulose21/2-acetate; polyacrylonitrile, synthetic polyamides such ashexamethylene-diamine adipate, poly-ε-caprolactam or 4-aminoundecanicacid; and polyurethanes. The fibre materials may be present in the mostvaried stages of processing, for example, as threads, loose material,combed material, yarn, as piece goods such as fabrics or knittedfabrics, or as ready-made goods.

Dyeing according to the invention is preferably carried out in closedapparatus, for example, by introducing the fibre materials at roomtemperature into the dyebath, heating the dyebath to 60° - 170° C andkeeping it at this temperature until the bath is exhausted; this isusually the case after 10 - 60 minutes. After cooling to roomtemperature, the liquor is separated and the fibre materials are freedfrom any adhering solvent, optionally after a short rinsing with freshorganic solvent, by filtering with suction or by centrifuging andsubsequent drying in a warm current of air. With the aid of the processaccording to the invention it is possible to dye synthetic fibrematerials from organic solvents in a simple way, high dyestuff yieldsand excellent fastness properties being achieved.

The sulphonamide group-containing dyestuffs to be used according to theinvention are largely insoluble in the organic water-immisciblesolvents. They are distinguished from the dyestuffs hitherto used fordyeing synthetic fibre materials from organic solvents by theirsubstantially better affinity and an increased fastness to sublimation.

It may be mentioned that mixtures of the dyestuffs to be used accordingto the invention sometimes give a better dyestuff yield than theindividual dyestuffs.

The parts given in the following Examples are parts by weight.

EXAMPLE 1

100 Parts of a fabric of textured polyethylene terephthalate fibres areintroduced at room temperature, without previous cleaning, into adyebath prepared from

1 part of the monoazo dyestuff 4-aminobenzene-sulphonic acid amide →3-methyl-pyrazolone-(5) and

1000 parts tetrachloroethylene.

The bath is heated to 115° C within 10 minutes and kept at the sametemperature for 30 minutes, while the liquor is vividly circulating. Theliquor is then separated and the dyed material is rinsed with freshsolvent at about 40° C for 5 minutes. After separating of the rinsingliquor, the dyed material is centrifuged and dried in an air current. Astrong yellow dyeing of excellent fastness to sublimation and very goodfastness to washing and light is obtained.

An equally satisfactory yellow dyeing was obtained in the same way on afabric of polycyclohexane-dimethylene terephthalate fibres.

Yellow dyeings of equally satisfactory fastness properties were alsoobtained when the dyestuff mentioned above was replaced with the sameamount of one of the following monoazo dyestuffs:

    __________________________________________________________________________    Example                                                                            Dyestuff                 Shade                                           __________________________________________________________________________     2   3-nitro-4-amino-benzene-sulphonic acid                                                                 yellow                                                ##STR37##                                                                3   2-amino-benzene-sulphonic acid amide                                                                   yellow                                                ##STR38##                                                                4                                                                                  ##STR39##               yellow                                               5-pyrazolone-1-sulphonic acid amide                                       5                                                                                  ##STR40##               yellow                                               1-sulphonic acid methylamide                                              6   4-methoxy-3-amino-benzene-sulphonic acid                                                               yellow                                                ##STR41##                                                                    6-pyrazolone                                                              7   3-nitro-4-amino-benzene-sulphonic acid                                                                 orange                                                ##STR42##                                                                    pyrazole                                                                  8                                                                                  ##STR43##               orange                                               lino-sulphonyl-phenyl)-3-ethoxy-5-amino-                                      pyrazole                                                                  9   4-amino-benzene-sulphonic acid amide                                                                   yellow                                                ##STR44##                                                                    acid ethyl ester                                                         10   4-amino-benzene-sulphonic acid amide                                                                   yellow                                                ##STR45##                                                                    pyrazolone                                                               11   4-amino-benzene-sulphonic acid ethylamide                                                              yellow                                                ##STR46##                                                                    acid                                                                     12   4-amino-benzene-sulphonic acid dimethyl-                                                               yellow                                                ##STR47##                                                                    carboxylic acid amide                                                    13   3-nitro-4-amino-benzene-sulphonic acid                                                                 yellow                                                ##STR48##                                                                    carboxylic acid ethyl ester                                              14                                                                                  ##STR49##               yellow                                               sulphonyl-phenyl)-3-methyl-5-pyrazolone                                  15   4-amino-benzene-sulphonic acid-(di-2-                                                                  yellow                                                ##STR50##                                                                    3-methyl-5-pyrazolone                                                    16   4-amino-benzene-sulphonic acid ethylamide                                                              yellow                                                ##STR51##                                                                    pyrazolone                                                               17                                                                                  ##STR52##               yellow                                               sulphonyl-phenyl)-3-methyl-5-pyrazolone                                  18                                                                                  ##STR53##               yellow                                               sulphonyl-phenyl)-3-methyl-5-pyrazolone                                  19   4-amino-benzene-sulphonic acid-dimethyl-                                                               yellow                                                ##STR54##                                                                    methyl-5-pyrazolone                                                      20   3-nitro-4-amino-benzene-sulphonic acid                                                                 yellow                                                ##STR55##                                                                    pyrazolone-3-carboxylic acid                                             21                                                                                  ##STR56##               yellow                                               sulphonyl-ethyl)-3-methyl-5-pyrazolone                                   22                                                                                  ##STR57##               yellow                                               benzene-2-sulphonic acid-(di-2-cyanoethyl)-                                   amide                                                                    23                                                                                  ##STR58##               yellow                                               benzene-2-sulphonic acid-(4-chlorophenyl)-                                    amide                                                                    24   4-(4-pyrrolidinosulphonylbutoxy)-aniline                                                               yellow                                                ##STR59##                                                                    (2-pyridino)-amide                                                       25                                                                                  ##STR60##               yellow                                               benzene-2-sulphonic acid-(3-sulpholanyl)-                                     amide                                                                    26   4-amino-benzene-sulphonic acid amide                                                                   yellow                                                ##STR61##                                                               27   2-amino-benzene-sulphonic acid amide                                                                   yellow                                                ##STR62##                                                               28   3-nitro-4-amino-benzene-sulphonic acid amide                                                           yellow                                                ##STR63##                                                               29   3-nitro-5-chloro-4-amino-benzene-                                                                      yellow                                                ##STR64##                                                               30   4-amino-benzene-sulphonic acid-piperidide                                                              yellow                                                ##STR65##                                                                    carboxylic acid                                                          31   4-amino-benzene-sulphonic acid-(2-methyl-                                                              yellow                                                ##STR66##                                                                    methyl-benzene-2-sulphonic acid amide                                    32                                                                                  ##STR67##               yellow                                               hydroxy-4-n-propyl-benzene                                               33                                                                                  ##STR68##               yellow                                               hydroxy-4-methyl-benzene                                                 34   4-dimethylamino-sulphonylamino-aniline                                                                 yellow                                                ##STR69##                                                               35   4-methylsulphonylamino-aniline                                                                         yellow                                                ##STR70##                                                                    carboxylic acid amide                                                    __________________________________________________________________________

EXAMPLE 36

100 Parts of a fabric of triacetate fibres are introduced at roomtemperature into a dyebath prepared from

1 part of the monoazo dyestuff 4-methyl-sulphonylamino-aniline →1-hydroxy-4-methyl-benzene and

1000 parts tetrachloroethylene.

The bath is heated to 110° C within 20 minutes and kept at the sametemperature for 45 minutes while the liquor is vividly circulating. Theliquor is then separated and the fabric is rinsed with freshtetrachloroethylene at 40° C. After separation of the rinsing liquor,the dyed materials is freed from the adhering solvent by centrifugingand drying in an air current. A full brilliant yellow dyeing ofexcellent fastness properties is obtained.

EXAMPLE 37

100 Parts of yarn of acetate threads are introduced at about 22° C intoa dyebath prepared from

1 part of the monoazo dyestuff 4-piperidyl-sulphonylamino-aniline →1-hydroxy-4-methyl-benzene,

1000 parts tetrachloroethylene

1.5 parts oleic acid ethanolamide

1.5 parts oleyl alcohol eicosaethylene glycol ether and

6 parts of water.

The bath is heated to 78° C within 20 minutes and kept at the sametemperature for 45 minutes. After separation of the dye liquor andrinsing with fresh tetrachloroethylene, the dyed material is freed fromthe adhering solvent by filtering with suction and drying in an aircurrent. A brilliant yellow dyeing is obtained.

EXAMPLE 38

100 Parts of yarn of polyacrylonitrile fibres are dyed in a dyebathprepared as described in Example 36. The bath is heated to 100° C within20 minutes and kept at the same temperature for 30 minutes. After theusual washing and drying, there is obtained a yellow dyeing of goodfastness properties.

EXAMPLE 39

100 Parts of a fabric of polyethylene terephthalate fibres are heated ina dyebath containing

1 part of the monoazo dyestuff 3-nitro-4-aminobenzene-sulphonic acidamide → 1-methyl-2,4-dihydroxy-quinoline in

1000 parts tetrachloroethylene

to 115° C within 10 minutes and dyed at the same temperature for 30minutes. After separation of the liquor, rinsing and drying, there isobtained a brilliant greenish yellow dyeing of very good fastness tosublimation, washing and light.

When the above dyestuff was replaced with the same amount of one of thedyestuffs listed in the following Table, dyeings of equally satisfactoryfastness properties were obtained in the shades stated in the Table:

    __________________________________________________________________________    Example                                                                            Dyestuff                 Shade                                           __________________________________________________________________________    40   4-amino-benzene-sulphonic acid amide                                                                   yellow                                                ##STR71##                                                               41   4-trifluoromethyl-2-amino-benzene-                                                                     yellow                                                ##STR72##                                                                    dihydroxy-quinoline                                                      42   4-chloro-3-amino-benzene-sulphonic acid                                                                yellow                                                ##STR73##                                                                    dihydroxy-quinoline                                                      43   4-amino-benzene-sulphonic acid-(di-2-                                                                  yellow                                                ##STR74##                                                                    dihydroxy-quinoline                                                      44   3-amino-benzene-sulphonic acid-(2-methyl-                                                              yellow                                                ##STR75##                                                                    dihydroxy-quinoline                                                      45   4-amino-benzene-sulphonic acid-(1-naphthyl)-                                                           yellow                                                ##STR76##                                                               46   3,5-dichloro-4-amino-benzene-sulphonic acid                                                            yellow                                                ##STR77##                                                                    ethyl-aniline                                                            47   3,6-dichloro-4-amino-benzene-sulphonic acid                                                            orange                                                ##STR78##                                                                    ethyl-aniline                                                            48   3-nitro-4-amino-benzene-sulphonic acid amide                                                           reddish                                               ##STR79##               yellow                                          49   3-nitro-5-bromo-4-amino-benzene-sulphonic                                                              yellowish                                             ##STR80##               red                                                  aniline                                                                  50   3-nitro-4-amino-benzene-sulphonic acid                                                                 reddish                                               ##STR81##               yellow                                               ethyl)-aniline                                                           51   3-cyano-5-nitro-4-amino-benzene-sulphonic                                                              yellowish                                             ##STR82##               red                                                  ethyl)-aniline                                                           52   3,5-dicyano-4-amino-benzene-sulphonic acid                                                             red                                                   ##STR83##                                                               53   3-chloro-5-nitro-2-amino-benzene-sulphonic                                                             red                                                   ##STR84##                                                                    ethyl)-aniline                                                           54   3-chloro-5-nitro-2-amino-benzene-sulphonic                                                             red                                                   ##STR85##                                                                    ethyl)-aniline                                                           55   3-cyano-5-nitro-2-amino-benzene-sulphonic                                                              bluish                                                ##STR86##               red                                                  methoxycarbonyloxy-ethyl)-aniline                                        56   3,5-dichloro-4-amino-benzene-sulphonic acid                                                            orange                                                ##STR87##                                                                    ethyl)-aniline                                                           57   3-cyano-5-bromo-4-amino-benzene-sulphonic                                                              reddish                                               ##STR88##               orange                                               phenylamino)-ethyl]-succinimide                                          58   5-methoxy-2-amino-benzene-sulphonic acid                                                               yellowish                                             ##STR89##               red                                                  ethyl)-aniline                                                           59   3-bromo-5-nitro-4-amino-benzene-sulphonic                                                              violet                                                ##STR90##                                                                    aniline                                                                  60   3-bromo-5-cyano-4-amino-benzene-sulphonic                                                              red-                                                  ##STR91##               violet                                               aniline                                                                  61   3,5-dicyano-4-amino-benzene-sulphonic acid                                                             violet                                                ##STR92##                                                               62   3-bromo-5-nitro-4-amino-benzene-sulphonic                                                              violet                                                ##STR93##                                                                    N,N-dimethyl-aniline                                                     63   3-chloro-5-nitro-2-amino-benzene-sulphonic                                                             violet                                                ##STR94##                                                                    N,N-dimethyl-aniline                                                      64                                                                                 ##STR95##               violet                                               sulphonylamino-N,N-dimethylaniline                                       65   2-bromo-4-nitro-6-cyano-aniline                                                                        blue-                                                 ##STR96##               violet                                               N-(2-cyanoethyl)-aniline                                                  66                                                                                 ##STR97##               blue                                                 3-methylsulphonylamino-N,N-dimethyl-                                          aniline                                                                   67                                                                                 ##STR98##               violet                                               sulphonylamino-N,N-dimethyl-aniline                                       68                                                                                 ##STR99##               violet                                               3-methylsylphonylamino-N-(2-hydroxy-                                          ethyl)-N-(2-cyanoethyl)-aniline                                           69                                                                                 ##STR100##              blue                                                 5-methylsulphonylamino-N,N-(di-2-                                             acetoxymethyl)-aniline                                                    70                                                                                 ##STR101##              reddish                                              sulphonyl-amino-N,N-(di-2-acetoxy-                                                                     yellow                                               ethyl)-aniline                                                           71   3-bromo-5-nitro-4-amino-benzene-                                                                       brown                                                 ##STR102##                                                                   sulphonylmethylamino-N,N-dimethyl-                                            aniline                                                                   72                                                                                 ##STR103##              brown                                                3-(3-ethylaminosulphonylpropylamino)-                                         N,N-diethyl-aniline                                                       73                                                                                 ##STR104##              yellow-                                              N-ethyl-N-(2-dimethylaminosulphonyl-                                                                   brown                                                ethyl)-aniline                                                            74                                                                                 ##STR105##              reddish                                              3-methyl-N,N-(di-2-acetoxyethyl)-                                                                      yellow                                               aniline                                                                  75   3-nitro-5-amino-benzene-sulphonic acid                                                                 orange                                                ##STR106##                                                                   ethyl)-N-(2-methoxycarbonylethyl)-                                            anilino                                                                   76                                                                                 ##STR107##              yellow                                               sulphonyl-aniline                                                         77                                                                                 ##STR108##              reddish                                              ethyl-N-(2-methylsulphonylamino-                                                                       yellow                                               ethyl)-aniline                                                           78   4-amino-benzene-sulphonic acid methyl-                                                                 yellow                                                ##STR109##                                                              79   4-amino-benzene-sulphonic acid-thio-                                                                   yellow                                               morpholid-8-dioxide                                                      80   4-(3-methylaminosulphonyl-benzoyl-                                                                     yellow                                                ##STR110##                                                              81   6-methylaminosulphonyl-2-amino-1,3-                                                                    red                                                   ##STR111##                                                                   (2-acetoxyethyl)-aniline                                                 82   6-aminosulphonyl-2-amino-1,3-benzo-                                                                    red                                                   ##STR112##                                                                   aniline                                                                  83   3-chloro-4-amino-benzene-sulphonic acid                                                                orange                                                ##STR113##                                                                   aniline                                                                  84   5-methylaminosulphonyl-2-amino-                                                                        bluish                                                ##STR114##              red                                                  ethyl)-aniline                                                           85   5-aminosulphonyl-2-amino-1,3-                                                                          red-                                                  ##STR115##              violet                                               aniline                                                                  86   4-(4-aminosulphonylphenyl)-2-amino-                                                                    yellowish                                             ##STR116##              red                                                  ethyl)-aniline                                                           87   4-(4-methylaminosulphonylphenyl)-2-                                                                    red                                                   ##STR117##                                                                   amino-N,N-dimethyl-aniline                                                88                                                                                 ##STR118##              orange                                               3-methyl-N,N-(di-2-acetoxyethyl)-                                             aniline                                                                   89                                                                                 ##STR119##              reddish                                              3-acetylamino-aniline    orange                                           90                                                                                 ##STR120##              red                                                  naphthalene-6-sulphonic acid methylamide                                  91                                                                                 ##STR121##              red                                                  naphthalene-6-sulphonic acid amide                                       92   4-methylsulphonylamino-2-nitro-aniline                                                                 red                                                   ##STR122##                                                               93                                                                                 ##STR123##              red                                                  2-aminonaphthalene-5-sulphonic acid                                           methylamide                                                               94                                                                                 ##STR124##              yellow                                               1,2-dimethyl-indole                                                       95                                                                                 ##STR125##              red                                                  naphthalene-6-sulphonic acid-N-methyl-                                        N-(2-hydroxyethyl)-amide                                                  96                                                                                 ##STR126##              red                                                  naphthalene-6-sulphonic acid-N-methyl-                                        N-(2-acetoxyethyl)-amide                                                 97   4-amino-azobenzene-4'-sulphonic acid amide                                                             red                                                   ##STR127##                                                              98   3-chloro-5-amino-benzene-sulphonic acid                                                                reddish                                               ##STR128##              yellow                                          99   4-methyl-5-aminosulphonyl-2-amino-1,3-                                                                 red                                                   ##STR129##                                                                   aniline                                                                  100  5-nitro-3-amino-benzoisothiazole-(2,1)                                                                 navy                                                  ##STR130##                                                                   aniline                                                                  101  5-nitro-3-amino-benzoisothiazole-(2,1)-                                                                red                                                   ##STR131##                                                                   N,N-dimethyl-aniline                                                     __________________________________________________________________________

EXAMPLE 102

100 Parts of a knitted fabric of polyethylene terephthalate fibres aredyed in a dyebath containing

1 part of the disazo dyestuff 4-aminobenzene-sulphonic acid amide →aniline → phenol in

1000 parts tetrachloroethylene

at 115° C for 30 minutes. After the usual rinsing and drying, there isobtained a reddish yellow dyeing of very good fastness to sublimation,washing and light.

Dyeings of equally valuable fastness properties were also obtained whenthe above dyestuff was replaced with the same amount of one of thefollowing disazo dyestuffs:

    __________________________________________________________________________    Example                                                                            Dyestuff                 Shade                                           __________________________________________________________________________    103                                                                              4-amino-benzene-sulphonic acid methyl-                                                                   reddish                                             ##STR132##                 orange                                         104                                                                              3-chloro-4-amino-benzene-sulphonic acid                                                                  orange                                              ##STR133##                                                                 105                                                                              ##STR134##                 orange                                            1-hydroxy-benzene-2-sulphonic acid-(2-                                        hydroxyethyl)-amide                                                        106                                                                              4-chloro-3-amino-benzene-sulphonic acid                                                                  reddish                                             ##STR135##                 yellow                                         107                                                                              3-nitro-4-amino-benzene-sulphonic acid                                                                   reddish                                             ##STR136##                 yellow                                          108                                                                              ##STR137##                                                                                               ##STR138##                                      109                                                                              ##STR139##                 yellow                                          110                                                                              ##STR140##                 orange- brown                                   111                                                                              ##STR141##                 reddish yellow                                 112                                                                               ##STR142##                reddish yellow                                  113                                                                               ##STR143##                reddish yellow                                  114                                                                               ##STR144##                orange                                          115                                                                               ##STR145##                orange                                           116                                                                              ##STR146##                orange                                          117                                                                               ##STR147##                reddish yellow                                   118                                                                              ##STR148##                 reddish yellow                                 119                                                                               ##STR149##                reddish yellow                                   120                                                                              ##STR150##                 reddish yellow                                  121                                                                              ##STR151##                 orange                                         __________________________________________________________________________

EXAMPLE 122

50 Parts of a fabric of polyester fibres are introduced at roomtemperature into a dyebath prepared from

1 part 1-amino-4-hydroxy-2-(4-aminosulphonyl-phenyl-thio-anthraquinone

1.5 parts oleic acid ethanolamide

1.5 parts oleyl alcohol eicosaethylene glycol ether

6 parts of water and

500 parts tetrachloroethylene.

The bath is heated to 120° C within 10 minutes and kept at the sametemperature for 45 minutes while the liquor is vividly circulating.After separation of the dye liquor, the dyed material is rinsed withfresh solvent at 40° C and, after removal of the rinsing liquor, driedin an air current. A brilliant violet dyeing of excellent fastness tolight and sublimation is obtained.

Equally satisfactory violet dyeings are obtained when the 500 partstetrachloroethylene are replaced with the same amount of1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane,1,1,2,2-tetrachloroethane, pentachloroethane, 1,2-dichloropropane,2-chlorobutane, 1,4-dichlorobutane, perfluoro-n-hexane,1,2,2-trifluoro-trichloroethane, trifluoro-pentachloropropane,chlorobenzene, fluorobenzene, chlorotoluene or benzotrifluoride.

The dyestuff used in Example 122 had been prepared as follows: 15 parts1-amino-4-hydroxy-2-phenylthioanthraquinone are dissolved in 76 partschlorosulphonic acid, and 22.5 parts thionyl chloride are added at20°-25° C within 1 hour. The melt is stirred at 20°- 25° C for 3 hours,turned out on to ice, the precipitate is filtered off with suction andwashed with ice-water until neutral. The product is subsequentlyintroduced into 250 parts of 25% ammonia and stirred at 20°-25° C for 5hours. It is filtered off with suction, washed with water, and afterdrying there are obtained 18.5 parts1-amino-4-hydroxy-2-(4-aminosulphonyl-phenylthio)-anthraquinone = 96% oftheory.

EXAMPLE 123

100 Parts of fibre yarn of poly-ε-caprolactam are introduced at roomtemperature into a dyebath containing

1 part of the dyestuff mentioned in Example 122 in 1000 partstetrachloroethylene.

The bath is heated to 100° C within 20 minutes and kept at the sametemperature for 40 minutes while the liquor is vividly circulating.After this period of time, the liquor is separated, the dyeing isbriefly rinsed with fresh solvent and dried in an air current aftercentrifuging. A brilliant violet dyeing of good fastness properties isobtained.

An equally satisfactory dyeing was also obtained on yarns ofpolyhexamethylene-diamine adipate fibres.

The strength of colour of the dyeing can be increased by ˜ 10% by theaddition of

1 part oleic acid ethanolamide

1 part oleyl alcohol eicosaethylene glycol ether and

4 parts of water

to the dyebath.

EXAMPLE 124

100 Parts polyethylene terephthalate fabric are dyed at 115° C for 30minutes in a dyebath consisting of

1 part1-amino-4-hydroxy-2-(4-methylamino-sulphonyl-phenoxy)-anthraquinone,

3 parts oleic acid ethanolamide

3 parts oleyl alcohol eicosaethylene glycol ether 12 parts of water and

1600 parts tetrachloroethylene.

After rinsing with fresh tetrachloroethylene and drying, there isobtained a strong and brilliant red dyeing of very good fastness tosublimation, washing and light.

When the above dyestuff was replaced with the same amount of one of thedyestuff listed in the following Table, then dyeings of equallysatisfactory fastness properties were obtained in the shades stated inthe Table:

    ______________________________________                                        Exam-                                                                         ple   Dyestuff                  Shade                                         ______________________________________                                        125   1-amino-4-hydroxy-2-[4-(2-methoxyethyl-                                                                 red                                                 amino)-sulphonyl-phenoxy]-anthraquinone                                 126   1-amino-4-hydroxy-2-[4-(2-hydroxyethyl-                                                                 red                                                 amino)-sulphonyl-phenoxy]-anthraquinone                                 127   1-amino-4-hydroxy-6-chloro-2-(4-amino-                                                                  red                                                 sulphonyl-phenoxy)-anthraquinone                                        128   1-amino-4-hydroxy-6,7-difluoro-2-                                                                       red                                                 (4-thiomorpholino-sulphonyl-phenoxy)-                                         anthraquinone                                                           129   1-amino-4-hydroxy-2-(4-methylsulphonyl-                                                                 red                                                 aminophenoxy)-anthraquinone                                             130   1-amino-4-hydroxy-2-[2-(4-aminosulphonyl-                                                               red                                                 phenoxy)-ethoxy]-anthraquinone                                          131   1-amino-4-hydroxy-2-[2-(4-methylamino-                                                                  red                                                 sulphonylphenyl)-ethoxy]-anthraquinone                                  132   1-amino-4-hydroxy-2-[4-aminosulphonyl                                                                   red                                                 phenylthio)-ethoxy-]anthraquinone                                       133   1-amino-4-hydroxy-2-(4-diethylamino-                                                                    red                                                 sulphonylamino-phenoxy)-anthraquinone                                   134   1-amino-4-hydroxy-2-[4-(3-methoxy-                                                                      violet                                              propylamino)-sulphonyl-phenyl-thio]-                                          anthraquinone                                                           135   1-amino-4-hydroxy-2-[4-(2-hydroxy-                                                                      violet                                              ethylamino)-sulphonyl-phenyl-thio]-                                           anthraquinone                                                           136   1-amino-4-hydroxy-2-[4-chloro-2-(di-2-                                                                  violet                                              hydroxyethyl)-amino-sulphonyl-phenyl-                                         thio]-anthraquinone                                                     137   1-amino-4-hydroxy-2-(4-methylthio-3-                                                                    violet                                              amino-sulphonyl-phenyl-thio)-anthra-                                          quinone                                                                 138   1-amino-4-hydroxy-7-chloro-2-[(2-methyl-                                                                violet                                              sulphonylethyl)-amino-sulphonyl-phenyl-                                       thio]-anthraquinone                                                     139   1-amino-4-hydroxy-2-(3-aminosulphonyl-                                                                  bluish                                              propylthio)-anthraquinone red                                           140   1-amino-4-hydroxy-2-(4-methylamino-                                                                     bluish                                              sulphonyl-benzylthio)-anthraquinone                                                                     red                                           141   1-amino-4-hydroxy-2-[2-(4-hexamethylene-                                                                bluish                                              imino-sulphonyl-phenyl)-ethylthio]-                                                                     red                                                 anthraquinone                                                           142   1-amino-4-hydroxy-2-[2-(3-methyl-4-                                                                     bluish                                              aminosulphonyl-phenoxy)-ethyl-thio]-                                                                    red                                                 anthraquinone                                                           143   1-amino-4-hydroxy-2-(2-dimethylamino-                                                                   bluish                                              sulphonylethylthio)-anthraquinone                                                                       red                                           144   1-amino-4-methoxy-2-(4-methylamino-                                                                     yellow-                                             sulphonyl-phenoxy)-anthraquinone                                                                        red                                           145   1-amino-4-methoxy-2-(4-N-methyl-N-                                                                      red                                                 phenylamino-sulphonyl-phenyl-thio)-                                           anthraquinone                                                           146   1-amino-2-(4-morpholinosulphonyl-                                                                       orange                                              phenoxy)-anthraquinone                                                  147   1-amino-2-(4-aminosulphonyl-phenyl-thio)-                                                               yellow-                                             anthraquinone             red                                           148   1,4-dihydroxy-2-[4-(2-cyanoethylamino)-                                                                 orange                                              sulphonyl-phenoxy]-anthraquinone                                        149   1,4-dihydroxy-2-(4-aminosulphonyl-phenoxy)-                                                             orange                                              anthraquinone                                                           150   1,4-dihydroxy-2-(4-methylamino-                                                                         scarlet                                             sulphonyl-phenyl-thio)-anthraquinone                                    151   1,4-diamino-2-[4-(3-cyano-phenyl-amino)-                                                                blue-                                               sulphonyl-phenoxy]-anthraquinone                                                                        violet                                        152   1,4-diamino-2,3-bis-(4-amino-sulphonyl-                                                                 red-                                                phenoxy)-anthraquinone    violet                                        153   1,4-diamino-2-(4-amino-sulphonyl-phenyl-                                                                reddish                                             thio)-anthraquinone       blue                                          154   1,4-diamino-2-[4-(3-methoxypropylamino)-                                                                reddish                                             sulphonyl-phenyl-sulphonyl]-anthraquinone                                                               blue                                          155   1,4-diamino-anthraquinone-2-sulphonic acid                                                              reddish                                             (4-ethyl-amino-sulphonyl-phenyl) ester                                                                  blue                                          156   1-hydroxy-4-(3-methylamino-sulphonyl-                                                                   blue-                                               phenyl-amino)-anthraquinone                                                                             violet                                        157   1-hydroxy-4-(4-methyl-3-amino-sulphonyl-                                                                blue-                                               phenyl-amino)-anthraquinone                                                                             violet                                        158   1-hydroxy-4-(4-methylsulphonyl-amino-                                                                   reddish                                             phenyl-amino)-anthraquinone                                                                             blue                                          159   1-amino-4-[4-(2-cyanoethyl-2-hydroxy-                                                                   blue                                                ethyl-amino-sulphonyl)-phenyl-amino]-                                         anthraquinone                                                           160   1-amino-4-(2,6-diethyl-4-methyl-3-                                                                      reddish                                             amino-sulphonyl-phenyl-amine)-anthra-                                                                   blue                                                quinone                                                                 161   1-amino-2-bromo-4-(4-methoxy-3-amino-                                                                   reddish                                             sulphonyl-phenylamino)-anthraquinone                                                                    blue                                          162   1-amino-2-phenyl-thio-4-(4-methyl-3-                                                                    blue                                                amino-sulphonyl-phenylamino)-anthra-                                          quinone                                                                 163   1-amino-2-phenyl-sulphonyl-4-(3-amino-                                                                  greenish                                            sulphonyl-phenylamino)-anthraquinone                                                                    blue                                          164   1-amino-4-(4-amino-sulphonyl-phenyl-                                                                    red                                                 thio)-anthraquinone                                                     165   1-amino-2-(4-amino-sulphonyl-phenoxy)-                                                                  pink                                                4-(4-methylphenyl)-sulphonyl-amino)-                                          anthraquinone                                                           166   1-amino-2-(4-amino-sulphonyl-phenoxy)-                                                                  pink                                                4-methyl-sulphonyl-amino-anthraquinone                                  167   1-amino-anthraquinone-2-sulphonic acid                                                                  red                                                 (4-methoxyphenyl-amide)                                                 168   1-amino-4-hydroxy-anthraquinone-2-                                                                      red                                                 sulphonic acid-(3-trifluoromethyl-phenyl-                                     amide)                                                                  169   1,4-diamino-anthraquinone-2-sulphonic acid                                                              blue                                                amide                                                                   170   1,4-diamino-anthraquinone-2-sulphonic acid                                                              blue                                                (2-methoxy-ethyl)-amide                                                 171   1,5-dihydroxy-4,8-diamino-anthraquinone-                                                                blue                                                2-sulphonic acid ethylamide                                             172   1,5-dihydroxy-4,8-diamino-anthraquinone-                                                                blue                                                2,6-disulphonic acid-(3-methoxypropyl)-                                       amide                                                                   173   1,4-diamino-2-[5-methylaminosulphonyl-                                                                  blue                                                benzoxazolyl-(2)]-anthraquinone                                         174   1-amino-4-(4-methylphenyl-amino)-                                                                       blue                                                anthraquinone-2-sulphonic acid-(2-hydroxy-                                    ethyl)-amide                                                            175   1-amino-4-cyclohexyl-amino-anthraquinone-                                                               blue                                                2-sulphonic acid amide                                                  176   1-(3-aminosulphonyl-propyl-amino)-                                                                      red                                                 anthraquinone                                                           177   1,4-bis-(3-amino-sulphonyl-propyl-                                                                      blue                                                amino)-anthraquinone                                                    178   1,5-dihydroxy-4,8-diamino-2-(4-hydroxy-                                                                 blue                                                3-ethylamino-sulphonyl-phenyl)-                                               anthraquinone                                                           179   1,5-dihydroxy-4,8-diamino-3-(4-hydroxy-                                                                 blue                                                3-methylamino-sulphonyl-phenyl)-anthra-                                       quinone                                                                 180   1,5-dihydroxy-8-nitro-4-(3-ethylamino-                                                                  blue                                                sulphonyl-phenylamino)-anthraquinone                                    181   1,8-dihydroxy-5-nitro-4-(3-amino-                                                                       blue                                                sulphonyl-phenylamino)-anthraquinone                                    182   1,5-dihydroxy-8-amino-4-(3-methylamino-                                                                 blue                                                sulphonyl-phenylamino)-anthraquinone -183                                                               1,8-dihydroxy-5-amino-4-(3-amino- blue              sulphonyl-phenylamino)-anthraquinone                                    184   1,5-dihydroxy-8-amino-x-chloro-4-                                                                       blue                                                (3-amino-sulphonyl-phenylamino)-                                              anthraquinone                                                           185   1,5-dihydroxy-8-nitro-x-bromo-4-                                                                        blue                                                (3-amino-sulphonyl-phenylamino)-                                              anthraquinone                                                           186   1,8-dihydroxy-5-amino-x-bromo-4-                                                                        blue                                                (3-amino-sulphonyl-phenylamino)-                                              anthraquinone                                                           187   1,8-dihydroxy-5-amino-x-bromo-4-                                                                        blue                                                (3-amino-sulphonyl-phenylamino)-                                              anthraquinone                                                           188   1,8-dihydroxy-5-methylamino-4-                                                                          blue                                                (4-methyl-3-amino-sulphonyl-phenyl-                                           amino)-anthraquinone                                                    189   1,9-isothiazolanthrone-2-sulphonic acid                                                                 yellow                                              (4-bromo-phenyl)-amide                                                  190   5-(2-aminosulphonyl-ethylamino)-1,9-                                                                    yellow                                              isothiazoloanthrone                                                     191   1,9-pyrazoloanthrone-2-sulphonic acid-N-                                                                yellow                                              (2-hydroxyethyl)-N-phenyl-amide                                         192   5-(2-amino-sulphonyl-ethylamino)-1,9-                                                                   yellow                                              pyrazoloanthrone                                                        193   4-(3-amino-sulphonylphenylamino)-                                                                       red                                                 N-methyl-1,9-anthrapyridone                                             194   7-(2-hydroxyethyl)-amino-sulphonyl-                                                                     red                                                 3,4-phthaloyl-acridone                                                  195   7-(3-methoxypropyl)-amino-sulphonyl-                                          2-amino-3,4-phthaloyl-acridone                                          196   1,8-naphthoylene-benzimidazole-Bz-3-                                                                    yellow                                              sulphonic acid methylamide                                              197   1,8-naphthoylene-benzimidazole-4-                                                                       yellow                                              sulphonic acid amide                                                    198   1,8-naphthoylene-benzimidazole-4,5-                                                                     yellow                                              dicarboxylic acid-(2-methoxy-ethylimide)-                                     Bz-3-sulphonic acid ethylamide                                          199   phthaloylene-(1,8-naphthopyrimidine)-                                                                   yellow                                              3- or 6-sulphonic acid amide                                            200   4-(3-amino-sulphonyl-phenyl-amino)-                                                                     yellow                                              1,9-isothiazolo-anthrone                                                201   5-(3-amino-sulphonyl-phenyl-amino)-                                                                     yellow                                              1,9-isothiazolo-anthrone                                                202   4-(3-methylamino-sulphonyl-phenyl-                                                                      yellow                                              amino)-1,9-pyrazolo-anthrone                                            203   5-[3-(2-methoxyethyl-amino-sulphonyl)-                                                                  yellow                                              phenyl-amino]-1,9-pyrazolo-anthrone                                     ______________________________________                                    

EXAMPLE 204

100 Parts polyethylene terephthalate filaments are dyed in a dyebathconsisting of

1 part 4-phenylamino-3-nitrobenzene-sulphonic acid amide

3 parts oleic acid ethanolamide

3 parts oleyl alcohol eicosaethylene glycol ether

12 parts of water and

1600 parts tetrachloroethylene

at 115° C for 30 minutes while the liquor is vividly circulating, theyare centrifuged and rinsed with tetrachloroethylene at 40° C for 5minutes. A strong greenish yellow dyeing of very good fastness tosublimation, washing and light is obtained.

An equally satisfactory dyeing is obtained when the tetrachloroethyleneis replaced with the same amount of 1,1,2-trichloroethane.

When 1 part 4-phenylamino-3-nitrobenzene-sulphonamide is replaced with amixture of 0.5 parts 4-phenylamino-3-nitrobenzene-sulphonic acid amideand 0.5 parts 4-(4-methoxy-phenylamino)-3-nitrobenzene-sulphonamide,then a somewhat more reddish strong dyeing is obtained.

Similar dyeings are also obtained when the polyethylene terephthalatefilaments are replaced with fibres of anion-modified polyethyleneterephthalate (Dacron 64) or anion-modified polyhexamethylene-diamineadipate (Nylon T 844).

The dyestuff used in Example 204 had been prepared as follows: 900 partsof n-butanol saturated with ammonia are mixed with 550 parts of 79%4-chloro-3-nitrobenzene sulphochloride and the mixture is stirred at55°-60° C for 1 hour. 200 Parts aniline were added and the mixture washeated to boiling temperature while slowly introducing ammonia, untilthe dyestuff formation was completed. After cooling, the crystallisedproduct was filtered off with suction, washed with methanol and waterand after drying there were obtained 460 parts4-phenylamino-3-nitrobenzene-sulphonic acid amide = 92% of theory; m.p.155° C.

EXAMPLE 205

100 Parts of polycarbonate filaments are dyed in a dyebath consisting of

1 part 4-(4-methoxy-phenylamino)-3-nitrobenzene-sulphonic acid amide

2.5 parts oleic acid ethanolamide

2.5 parts oleyl alcohol eicosaethylene glycol ether

10 parts of water and

1000 parts tetrachloroethylene

as described in Example 204. A yellow dyeing of very good fastness tosublimation, washing and light is obtained.

When the dyestuffs given in Examples 204 and 205 were replaced with thesame amount of one of the dyestuffs listed in the following Table, thendyeings of equally satisfactory fastness properties were obtained in theshades stated in the Table:

    __________________________________________________________________________    Example                                                                            Dyestuff                Shade                                            __________________________________________________________________________    206  4-(4-ethoxy-phenylamino)-3-nitro-                                                                     reddish                                               benzene-sulphonic acid methylamide                                                                    yellow                                           207  4-(2-methoxy-phenylamino)-3-nitro-                                                                    reddish                                               benzene-sulphonic acid dimethylamide                                                                  yellow                                           208  4-phenylamino-3-nitro-benzene-sulphonic                                                               yellow                                                acid-(di-2-hydroxyethyl)-amide                                           209  4-(4-phenyl-phenylamino)-3-nitro-                                                                     yellow                                                benzene-sulphonic acid amide                                             210  4-(4-phenoxy-phenylamino)-3-nitro-                                                                    reddish                                               benzene-sulphonic acid  yellow                                           211  4-(4-azobenzeneamino)-3-nitro-benzene-                                                                reddish                                               sulphonic acid-(di-2-hydroxyethyl-amide                                                               yellow                                           212  4-[4-(2-hydroxyethoxy)-phenylamino]-                                                                  reddish                                               3-nitro-benzene-sulphonic acid phenyl-                                                                yellow                                                amide                                                                    213  4-(4-benzyloxy-phenylamino)-3-nitro-                                                                  reddish                                               benzene-sulphonic acid morpholide                                                                     yellow                                           214  4-(3-methoxy-phenylamino)-3-nitro-                                                                    reddish                                               benzene-sulphonic acid-(4-aminosulphonyl-                                                             yellow                                                phenyl)-amide                                                            215  4-(4-methoxycarbonyl-phenylamino)-3-                                                                  greenish                                              nitro-benzene-sulphonic acid-(2-hydroxy-                                                              yellow                                                ethyl)-amide                                                             216  4-(2,4-dimethoxy-phenylamino)-3-nitro-                                                                reddish                                               benzene-sulphonic acid amide                                                                          yellow                                           217  4-(4-carboxy-phenylamino)-3-nitro-                                                                    greenish                                              benzene-sulphonic acid ethylamide                                                                     yellow                                           218  4-[4-(2-hydroxyethyl-aminosulphonyl)-                                                                 greenish                                              phenylamino]-benzene-sulphonic acid-                                                                  yellow                                                (2-hydroxyethyl)-amide                                                   219  4-(3-fluoro-phenylamino)-3-nitro-                                                                     greenish                                              benzene-sulphonic acid-(2-methoxyethyl)-                                                              yellow                                                amide                                                                    220  4-(3-trifluoromethyl-phenylamino)-3-                                                                  greenish                                              nitro-benzene-sulphonic acid-(2-cyano-                                                                yellow                                                ethyl)-amide                                                             221  4-(3,4-dichloro-phenylamino)-3-nitro-                                                                 greenish                                              benzene-sulphonic acid-(3-methoxypropyl)-                                                             yellow                                                amide                                                                    222  4-(3-cyano-phenylamino)-3-nitro-                                                                      yellow                                                benzene-sulphonic acid-(4-methylamino-                                        carbonyl-phenyl)-amide                                                   223  4-(2-nitro-phenylamino)-3-nitro-                                                                      greenish                                              benzene-sulphonic acid piperidide                                                                     yellow                                           224  4-(4-methyl-phenylamino)-3-nitro-                                                                     yellow                                                benzene-sulphonic acid amide                                             225  4-(4-ethyl-phenylamino)-3-nitro-                                                                      yellow                                                benzene-sulphonic acid[4-(2-hydroxy-                                          ethoxy)-phenyl]-amide                                                    226  4-(4-aminosulphonyl-phenylamino)-3-                                                                   greenish                                              nitro-benzene-sulphonic acid-(di-2-hydroxy-                                                           yellow                                                ethyl)-amide                                                             227  4-(4-aminosulphonyl-phenylamino)-3-                                                                   greenish                                              nitro-benzene-sulphonic acid-(3-diethyl-                                                              yellow                                                amino-sulphonyl-phenyl)-amide                                            228  4-(4-acetylamino-phenylamino)-3-                                                                      yellow                                                nitro-benzene-sulphonic acid ethylamide                                  229  4-(4-methylsulphonylamino-phenylamino)-                                                               yellow                                                3-nitro-benzene-sulphonic acid phenylamide                               230  4-(4-methylsulphonylamino-phenylamino)-                                                               yellow                                                3-nitro-benzene-sulphonic acid-(2-hydroxy-                                    ethyl)-amide                                                             231  4-phenylamino-3-nitro-benzene-sulphonic                                                               greenish                                              acid-(4-aminosulphonyl-phenyl)-amide                                                                  yellow                                           232  4-(4-methoxy-phenylamino)-3-nitro-                                                                    reddish                                               benzene-sulphonic acid-(3-methylamino-                                                                yellow                                                sulphonyl-phenyl)-amide                                                  233  4-(4-ethoxy-phenylamino)-3-nitro-                                                                     reddish                                               benzene-sulphonic acid-[3-(2-cyanoethyl-                                                              yellow                                                aminosulphonyl)-phenyl]-amide                                            234  4-(4-methyl-phenylamino)-3-nitro-                                                                     yellow                                                benzene-sulphonic acid-(4-aminosulphonyl-                                     phenyl)-amide                                                            235  4-(3-trifluoromethyl-phenylamino)-3-                                                                  greenish                                              nitro-benzene-sulphonic acid-[ 3-(2-cyano-                                                            yellow                                                ethyl-2-hydroxyethyl-aminosulphonyl)-                                         phenyl]-amide                                                            236  4-phenylamino-3-nitro-benzene-sulphonic                                                               greenish                                              acid-[4-(2-aminosulphonylethoxy)-phenyl]-                                                             yellow                                                amide                                                                    237  4-[4-(3-aminosulphonyl-propoxy)-                                                                      reddish                                               phenyl-amino]-3-nitro-benzene-sulphonic                                                               yellow                                                acid-(3-chloro-phenyl)-amide                                             238  4-phenylamino-3-nitro-benzene-sulphonic                                                               yellow                                                acid-(4-aminosulphonyl-phenyl) ester                                     239  4-(4-methoxy-phenylamino)-3-nitrobenzene-                                                             reddish                                               sulphonic acid-(3-methylamino-sulphonyl-                                                              yellow                                                phenyl) ester                                                            240  4-(3-ethoxy-phenylamino)-3-nitrobenzene-                                                              reddish                                               sulphonic acid-[4-(di-2-hydroxy-ethyl-                                                                yellow                                                sulphonylamino)-phenyl] ester                                            241  4-(4-aminocarbonyl-phenylamino)-3-                                                                    greenish                                              nitrobenzene-sulphonic acid-(4-ethylamino-                                                            yellow                                                sulphonyl-phenyl) ester                                                  242  4-(3-acetylamino-phenylamino)-3-nitro-                                                                yellow                                                benzene-sulphonic acid-(4-aminosulphonyl-                                     phenyl) ester                                                            243  4-phenylamino-3-nitro-benzoic acid                                                                    yellow                                                (4-aminosulphonyl-phenyl) amide                                          244  4-(4-ethoxyphenylamino)-3-nitro-                                                                      reddish                                               benzoic acid-[3-(2-hydroxyethylamino-                                                                 yellow                                                sulphonyl)-phenyl]-amide                                                 245  4-(2,4-dimethoxy-phenylamino)-3-nitro-                                                                reddish                                               benzoic acid-(4-methylaminosulphonyl-                                                                 yellow                                                phenyl)-amide                                                            246  4-(4-methyl-phenylamino)-3-nitro-                                                                     yellow                                                benzoic acid-(3-methylaminosulphonyl-                                         phenyl)-amide                                                            247  4-(4-nitro-phenylamino)-3-nitro-                                                                      yellow                                                benzoic acid-(3-pyrrolidinosulphonyl-                                         phenyl)-amide                                                            248  4-(3-bromo-phenylamino)-3-nitro-                                                                      yellow                                                benzoic acid-(4-hydroxy-3-n-propyl-                                           amino-sulphonyl-phenyl)-amide                                            249  4-(4-acetylamino-phenylamino)-3-nitro-                                                                yellow                                                benzoic acid-(4-thiomorpholinosulphonyl-                                      phenyl)-amide                                                            250  4-(4-methylsulphonylamino-phenylamino)-                                                               yellow                                                3-nitro-benzoic acid-(3-dimethylamino-                                        sulphonyl-phenyl)-amide                                                  251  4-phenylamino-3-nitro-benzoic acid-(4-                                                                yellow                                                aminosulphonyl-phenyl) ester                                             252  4-(4-methoxy-phenylamino)-3-nitro-                                                                    yellow                                                benzoic acid-(3-methylaminosulphonyl-                                         phenyl) ester                                                            253  4-(3-methylsulphonylamino-phenylamino)-                                                               yellow                                                3-nitro-benzoic acid-[4-(3-hydroxypropyl-                                     aminosulphonyl)-phenyl] ester                                            254  4-(4-methylsulphonyl-phenylamino)-3-                                                                  greenish                                              nitro-benzene sulphonic acid-4-(amino-                                                                yellow                                                sulphonyl-phenyl)-amide                                                  255  4-(4-methylsulphonyl-phenylamino)-3-nitro-                                                            greenish                                              benzene sulphonic acid-(2-hydroxyethyl)-                                                              yellow                                                amide                                                                    256  4-(3-hydroxymethyl-phenylamino)-3-                                                                    yellow                                                nitro-benzene-sulphonic acid-(4-methyl-                                       amino-sulphonyl-phenyl)-amide                                            257  4-(3-hydroxymethylphenylamino)-3-                                                                     yellow                                                nitro-benzene-sulphonic acid-morpholide                                  258  4-(4-hydroxyethyl-phenylamino)-3-nitro-                                                               yellow                                                benzene-sulphonic acid-(3-aminosulphonyl-                                     phenyl)-amide                                                            259  4-(4-hydroxyethyl-phenylamino)-3-nitro-                                                               yellow                                                benzene-sulphonic acid amide                                             __________________________________________________________________________

EXAMPLE 260

100 Parts of yarn of polyethylene terephthalate fibres are dyed in adyebath consisting of

1 part of the quinophthalone dyestuff of the formula ##STR152##

2.5 parts oleic acid ethanolamide

2.5 parts oleyl alcohol

10 parts of water and

1600 parts tetrachloroethylene

as described in Example 204. A clear yellow dyeing is obtained, which ischaracterised by good fastness to sublimation, washing and light.

An equally satisfactory dyeing is obtained when the abovequinophthalone-sulphonamide dyestuff is replaced with a brominationproduct which contains about 1 bromine atom per molecule and can beobtained in known manner by bromination in nitrobenzene or glacialacetic acid.

Clear yellow dyeings are also obtained when the dyestuff mentioned inExample 260 is replaced with equal amounts of thequinophthalone-sulphonic acid amides listed in the following Table:

    __________________________________________________________________________     ##STR153##                                                                    Example                                                                             R.sub.1  R.sub.2                                                                          R.sub.3                                                                            ##STR154##                                            __________________________________________________________________________    261   H        H  H    NHCH.sub.3                                             262   H        H  H    N(CH.sub.3).sub.2                                      263   H        H  H    NHC.sub.2 H.sub.5                                      264   H        H  H    NHCH.sub.2CH.sub.2OH                                   265   H        H  H    N(CH.sub.2CH.sub.2OH).sub.2                            266   H        H  H    NHCH.sub.2CH.sub.2CN                                   267   Cl       H  H                                                                                   ##STR155##                                            268   Br       H  H    NH.sub.2                                               269   Cl       Cl H    NHCH.sub.3                                             270   NO.sub.2 H  H    NH.sub.2                                               271   CH.sub.3 O                                                                             H  H    NHCH.sub.2CH.sub.2OH                                   272   CH.sub.3 . CO . NH                                                                     H  H    N(CH.sub.3).sub.2                                      273   H        H  CH.sub.3                                                                           NH.sub.2                                               274   H        H  CH.sub.3 O                                                                         NH.sub.2                                               __________________________________________________________________________

Greenish yellow dyeings are obtained when thequinophthalone-sulphonamide dyestuff mentioned in Example 260 isreplaced with equal parts of one of the methine dyestuffs of theformulae ##STR156## or with a styryl dyestuff of the formula ##STR157##

EXAMPLE 275

100 Parts of a fabric of textured polyethylene terephthalate fibres areintroduced at room temperature, without previous cleaning, into adyebath prepared from

1 part 1-amino-4-hydroxy-2-[4-(4'-hydroxyanilinosulphonyl)-phenoxy]-anthraquinoneand

1000 parts tetrachloroethylene.

The bath is heated to 115° C within 10 minutes and kept at the sametemperature for 30 minutes, while the liquor is vividly circulating. Theliquor is then separated and the dyed material is rinsed with freshsolvent at about 40° C for 5 minutes. After separating of the rinsingliquor, the dyed material is centrifuged and dried in an air current.

There is obtained a strong red dyeing of excellent fastness to washing,light, rubbing and sublimation.

An equivalent red dyeing was obtained in the same way on a knittedfabric of poly-ε-caprolactame.

EXAMPLE 276

50 Parts of a fabric of polyester fibres are introduced at roomtemperature into a dyebath prepared from

1 part1-amino-4-hydroxy-2-[4-(4'-hydroxyanilinosulphonyl)-phenoxy]-anthraquinoneand

1,5 parts oleic acid ethanolamide

1,5 parts oleyl alcohol eicosaethylene glycol ether

6 parts of water and

500 parts tetrachloroethylene.

The bath is heated to 120° C within 10 minutes and kept at the sametemperature for 45 minutes while the liquor is vividly circulating.After separation of the dye liquor, the dyed material is rinsed withfresh solvent at 40° C and, after removal of the rinsing liquor, driedin an air current. A brilliant red dyeing of excellent fastness towashing, rubbing, light and sublimation is obtained.

EXAMPLE 277

100 parts of fibre yarn of poly-ε-caprolactame are introduced at roomtemperature into a dyebath containing

1 part1,4-diamino-2-[4-(4-hydroxyanilinosulphonyl)-phenylthio]-anthraquinonein

1000 parts tetrachloroethylene.

The bath is heated to 100° C within 20 minutes and kept at the sametemperature for 40 minutes while the liquor is vividly circulating.After this period of time, the liquor is separated, the dyeing isbriefly rinsed with fresh solvent and dried in an air current aftercentrifuging. A brilliant reddish blue dyeing of excellent fastness towashing, light, rubbing and sublimation is obtained.

An equivalent dyeing was obtained in the same manner on a yarn ofpoly-hexamethylene diamine adipate fibres.

EXAMPLE 278

100 Parts of a fabric of textured polyethylene terephthalate fibres areintroduced at room temperature, without previous cleaning, into adyebath prepared from

1 part 4-(4-hydroxyphenylamino)-3-nitro-benzenesulphonicacid-4-(hydroxyphenyl)-amide and

1000 parts tetrachloroethylene.

The bath is heated to 115° C within 10 minutes and kept at the sametemperature for 30 minutes, while the liquor is vividly circulating. Theliquor is then separated and the dyed material is rinsed with freshsolvent at about 40° C for 5 minutes. After separating of the rinsingliquor, the dyed material is centrifuged and dried in an air current. Astrong yellow dyeing of excellent fastness to washing, rubbing, lightand sublimation is obtained.

An equivalent yellow dyeing was obtained in the same manner on a fabricof poly-ε-caprolactame fibres.

EXAMPLE 279

50 Parts of a fabric of polyester fibres are introduced at roomtemperature into a dyebath prepared from

1 part 4-(4-hydroxyphenylamino)-3-nitro-benzenesulphonicacid-(4-hydroxyphenyl)-amide

1,5 parts oleic acid ethanolamide

1,5 parts oleyl alcohol eicosaethylene glycol ether

6 parts of water and

500 parts tetrachloroethylene.

The bath is heated at 120° C within 10 minutes and kept at the sametemperature for 45 minutes while the liquor is vividly circulating.After separation of the dye liquor, the dyed material is rinsed withfresh solvent at 40° C and, after removal of the rinsing liquor, driedin an air current. A brilliant yellow dyeing of excellent fastness towashing, rubbing, light and sublimation is obtained.

We claim:
 1. A process for dyeing synthetic fiber material by exhaustioncomprising introducing synthetic fiber material into a dyebath which isa dispersion consisting essentially ofA. organic solvent; B. nitrodyestuff containing 1 to 3 sulfonamide groups and largely insoluble insaid dyebath; and C. up to 1% by weight of said organic solvent ofwater; said organic solvent consisting of water immiscible aliphatichalogenated hydrocarbon; and dyeing at a temperature of 60° to 170° Cfor 10-60 minutes until the dyebath is exhausted;said nitro dyestufffree of reactive groups, acid groups and carboxamide groups having theformula ##STR158## in which R₁ means hydrogen, a halogen atom, atrifluoro, cyano, hydroxy, C₁ -C₄ -alkyl or -alkoxy, a hydromethyl or-ethyl, a hydroxy-ethylene-oxy, acylamino, alkylsulphonylamino,alkylsulphone, carboxamido, aminosulphonylalkylene-amino or sulphonamidegroup; R₂ means hydrogen or a C₁ -C₄ -alkoxy group; R₃ means hydrogen, ahalogen atom, a hydroxy, hydroxyethylene-oxy, carboxamido,aminosulphonyl-alkylene-oxy or sulphonamide group; X stands for thegroup --SO₂ -- or --CO; and Y stands for --NH-- or --O--,with theproviso that one of the radicals R₁, R₃ or ##STR159## is a sulphonamidegroup or a radical containing a sulphonamide group.
 2. Process of claim1 in which said nitro dyestuff has the formula ##STR160##
 3. Process fordyeing synthetic fiber material by exhaustion comprising introducingsynthetic fiber material into a dyebath which is a dispersion consistingessentially ofA. organic solvent; B. nitro dyestuff containing 1 to 3sulfonamide groups and largely insoluble in said dyebath; and C. up to1% by weight of said organic solvent of water; said organic solventconsisting of water immiscible aliphatic halogenated hydrocarbon; anddyeing at a temperature of 60° C to 170° C for 10-60 minutes until thedyebath is exhausted;said nitro dyestuff free of reactive groups, acidgroups and carboxamide groups having the formula ##STR161## in which R₁means hydrogen, a C₁ -C₄ -alkyl or -alkoxy group, halogen, atrifluoromethyl, nitro, hydroxymethyl, hydroxyethyl, phenyl, phenoxy,phenylazo, benzyloxy, carboxy, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄-acylamino, C₁ -C₄ -alkylsulphonyl or sulphonamide group; R₂ meanshydrogen, halogen or a C₁ -C₄ -alkoxy group; and D means a sulphonamidegroup.
 4. The process of claim 1 in which said synthetic fiber materialis polyester, polyamide, cellulose, triacetate, cellulose 21/2 acetate,polyacrylonitrile, or polyurethane.
 5. The process of claim 1 in whichsaid synthetic fiber material is polyester.
 6. The process of claim 1 inwhich said synthetic fiber material is polyamide.
 7. The process ofclaim 1 in which said dyebath contains 0.05 to 2% by weight of non-ionicdyeing auxiliary based on the weight of said aliphatic halogenatedhydrocarbon.